Thiophenyl-substituted quinophthalone dispersion dyestuffs

ABSTRACT

3-HYDROXY-QUINOPHTHALONE DYESTUFFS SUBSTITUTED IN THE 4-POSITION BY AN ETHER OR THIOETHER GROUP, AND A PROCESS FOR PREPARING THEM. SAID DYESTUFFS YIELD ON SYNTHETIC FIBROUS MATERIALS, ESPECIALLY THOSE FROM POLYETHYLENE TEREPHTALATES, YELLOW DYEINGS HAVING GOOD FASTNESS TO LIGHT, WET PROCESSING AND SOLVENTS AND A REMARKABLY GOOD FASTNESS TO THERMOFIXATION AND IRONING.

uaaea States Patent Oflice 3,823,147 Patented July 9, 1974 ABSTRACT OFTHE DISCLOSURE 3-Hydroxy-quinophtha1one dyestuffs substituted in the4-position by an ether or thioether group, and a process for preparingthem. Said dyestuifs yield on synthetic fibrous materials, especiallythose from polyethylene terephthalates, yellow dyeings having goodfastness to light, wet processing and solvents and a remarkably goodfastness to thermofixation and ironing.

4 Claims This application is a division of copending application Ser.No. 825,971, filed May 19, 1969. Said copending application is now Pat.No. 3,655,672, granted Apr. 11, 1972.

The present invention concerns quinophthalone dyestuffs corresponding tothe general formula in which X represents an oxygen or sulfur atom, Rrepresents an aryl radical, an aliphatic or cycloaliphatic radical or aheterocyclic ring, Y represents a hydrogen or halogen atom, a nitrogroup or a phenyl radical, Z stands for a hydrogen or halogen atom, m isan integer from 1 to 4 and n is 1 or 2. Moreover, this invention isconcerned with a process for preparing said dyestufis.

In German Auselgeschrift 1,168,862 compounds of the quinophthaloneseries are disclosed as suitable for dyeing polyester fibres.

From substituted quinophthalones 4-bromo-3-hydroxyquinophthalone, adyestuff of particular fastness to light in regard to polyester fibresand of moderate fastness to thermofixing is described in Britishspecifications Nos. 865,308 and 1,036,389.

It has now been found that new dyestuffs fast to thermofixationbelonging to the quinophthalone series and corresponding to the generalformula in which X represents an oxygen or sulfur atom, R represents anaryl radical, an aliphatic or cycloaliphatic radical or a heterocyclicring, Y reprents a hydrogen or halogen atom, a nitro group or a phenylradical, Z stands for a hydrogen or halogen atom, m is an integer from 1to 4 and n is one or two are obtained by reacting4-halogeno-3-hydroxy-quinophthalones of the general formula Q 0 Ye t":no

in which Q is a chlorine or bromine atom and Y, Z, m and n are definedas above;

(a) with compounds of the general formula RXH in which R and X have themeanings given above, in the presence of alkaline agents, or (b) withcompounds of the formula in which Me stands for an alkali metal atom ora radical of a tertiary base.

The aryl radical R in the above-identified formulae, preferably, is aphenyl, naphthyl, anthracenyl, fluorenyl, anthraquinonyl or pyrenylradical. Said radicals may carry one or more substituents such, forexample, as hydroxy, alkoxy, aryloxy, preferably phenoxy, nitro, keto,aldehyde, carboxyl, carboalkoxy, amino, alkyl, phenyl, naphthyl orbenzyl groups or halogen atoms. The aliphatic or cycloaliphatic radicalR which, preferably, is an alkyl or cycloalkyl group or the heterocyclicring R in the aforesaid formulae may likewise carry substituents, forexample, hydroxy, alkoxy, aryloxy, especially phenoxy, cyano, sulfonyl,amino or aryl groups, preferably phenyl or naphthyl groups or halogenatoms.

Suitable starting substances of the quinophthalone series are, forexample the following:

4-bromo-3-hydroxy-quinophthalone, 4-chloro-3-hydroxy-quinophthalone, 4,5',6'-tribromo-3-hydroxy-quinophthalone,4,4,5',6',7-pentabromo-3-hydroxy-quinophthalone,4-bromo-4',7-dichloro-3-hydroxy-quinophthalone,4-bromo-4',5',6',7-tetrachloro-3-hydroxy-quinophthalone,4-bromo-4'-fluoro-3-hydroxy-quinophthaolne,4-bromo-5-nitro-3-hydroxy-quinophthaolne,4,6-dibromo-3-hydroxy-quinophthalone,4-bromo-5,7-dichloro-3-hydroxy-quinophthalone, and4-bromo-5'-phenyl-3-hydroxy-quinophthalone.

As appropriate compounds of the formula RXH there may be named forexample phenol, alkyl phenols such as 4-hydroxytoluene, halophenols, forexample 4-bromophenol, 2 chlorophenol, 4 fiuorophenol, polyvalentphenols such as hydroquinone, hydroquino-monomethyl ether, nitrophenols,for example 4-nitro-phenol, hydroxyaldehdyes or ketones such as3-hydroxy-benzaldehyde, 4- hydroxy-acetophenone, hydroxy-carboxylicacids or esters, for example 4-hydroxy-benzoic acid, 4-hydroxy-benzoicacid ethyl ester, aminophenols such as 4-aminophenol, 4-methylamiuo-phenol, 4-dimethylamino-phenol, 4-hydroxydiphenylamine,hydroxy-diphenylmethane for example, 4- hydroxy-diphenyl-methane, 4,4"dihydroxy diphenylpropane (2,2), hydroxy-diaryls such as4-hydroxy-diphenyl, 2-hydroxy-diphenyl, naphthols, for example, 1-naphthol, 2-naphthol, halonaphtol for example, 2-chlorol-naphthol,4-bromo-1-naphthol, l-hydroxy-anthracene, 1- hydroxy-anthraquinone,9-hydroxyfiuorene, 3-hydroxypyrene alcohols such as methanol, ethanol,amylalochols, hexanol (1), dodecanol-( 1), ethylene glycol,diethylglycolhexandiol-(l,6), glycerin, ethyleneglycol-monoethyl ether,

3 diethylene-glycol-monoethyl-ether, 3-chloropropanol- 13-hydroxypropionitrile, chlorobenzene-4-fl-hydroxy-ethy1- sulfone,2-amino-ethanol-(1), Z-dimethylamino-ethanol- (1), benzylalcohol,hexahydro-benzyl alcohol heterocyclic hydroxy compounds such as6-hydroxyquinoline, 2-hydroxy pyridine, -nitro-Z-hydroxy-pyridine,1-(3'-hydroxyphenyl)-3-methyl-pyrazolone-(5), N-fl-hydroxyethylmorpholine, mercapto compounds, for example thiophenol,2,5-dichloro-thiophenol, 4-nonyl-thiophenol, thiophenol-2-carboxylicacid, 2-amino-3 mercaptotoluene, ethyl-mercaptane, dodecanthiol,5-nitro-2-mercapto-benz imidazol, S-mercapto-l-phenyl-tetrazol,Z-mercapto-benzoxazol and Z-mercapto-benzthiazol.

As alkaline media, for example alkali metal hydroxides such as sodium orpotassium hydroxide or anhydrous alkali metal carbonates, for examplesodium or potassium carbonate or anhydrous tertiary bases such astrimethyl amine or tributyl amine, may be used.

The reaction is suitably conducted in a nexcess of a hydroxy or mercaptocompound in the melt at or above melting temperature, advantageously inthe range of from 100 to 200 C., preferably 120 and 160 C. When no morestarting material can be ascertained in the melt, the mixture is pouredif desired or required after distilling off the excess of hydroxy ormercapto compound, in water or a lower alcohol. The precipitateddyestufi is drawn off, washed and dried.

In many cases it is advantageous to perform the reaction in a solvent.Appropriate solvents are those having a sufficient dissolving power foralkali metal salts of hydroxy or mercapto compounds. As such for exampledialkyl-formamides, for example dimethyl-formamide, N- alkyl-acetamidessuch as N-methyl-acetamide, phosphoric acid-tris-dialkylamide, forexample phosphoric acid trisdimethylamide and dialkyl sulfoxides, forexample dimethyl sulfoxide may be used. When applying one of thesesolvents it is of advantage to first form the salt from thecorresponding hydroxy or mercapto compound and the aklaline agent anddistill oif the water thus formed by means of an entraining agent. Asentraining agents aromatic or cycloaliphatic hydrocarbons, for exampletoluene, xylene or cyclohexane are suited. After the salt formation, theentraining agent itself is distilled off, the quinophthalone derivativeis added and the whole heated to the reaction temperature,advantageously 100-200 C., preferably 100-440 C. The course of thereaction is easy to follow by means of thin layer chromatography. Whenoperating with solvents the dyestufi is, advantageously isolated bypouring the reaction mixture in water, a dilute mineral acid or a loweralcohol and filtering off the precipitated dyestufl.

The dyestuifs obtained by the instant process yield on synthetic fibrousmaterials, especially those consisting of polyethylene terephthalates,yellow dyeings having good fastness to solvents and light and remarkablygood fastness to thermofixation and ironing. They are superior todyeings produced with 3-hydroxy-quinophthalone or 4-:bromo-3-hydroxy-quinophthalone in regard to better fastness tothermofixation.

In order to produce fast dyeings the polyester materials are treatedwith said dyestuffs in the presence of carriers at between -80 and 110C. or, in the absence thereof, at between 110 and 140 C. To produceprints, aqueous printing pastes are printed on the polyester tissuewhich is, subsequently steamed, in the presence of a carrier, at between95 and 110 C. or, without a carrier, at between 120 and 140 C.

The dyeing or printing may also be performed according to the so-calledthermosol process wherein the padded or printed fabric is subjected,shortly, to a treatment by dry heat at between 180 and 200 C.

The dyestuffs of the invention may likewise be'applied with good resultto dyeing polyethylene-terephthalates in the spinning solution.

The following Examples are to illustrate the invention but they are notintended to limit it thereto. The parts and percentages are by weightunless otherwise stated.

EXAMPLE 1 150 parts of phenol were melted and mixed at C., with 7.5parts of potassium hydroxide and '26 parts of 4-bromo-3-hydroxy-quinophthalone. This mixture was, subsequently, heatedto C. until no more starting substance was ascertained in a sample. Themelt was poured in 500 parts of methanol, the dyestutf was drawn off,washed with methanol and dried. 22 parts of 4-phenoxy-3-hydroxy-quinophthalone of the formula O 1!! HO sift) \C/ E were obtainedmelting at 244-246 C. The yield amounted to 82% of the theory. Thedyestulf dyed polyester fibres yellow shades having good fastness tolight and wet processing and remarkably good fastness to thermofixation.

EXAMPLE 2 15 parts of 4-hydroxy-toluene, 7.5 parts of potassiumhydroxide, parts of dimethyl-formamide and 100 partsand melting at 265-266 C. Were obtained, a yield amounting to 79% of the theory. Thedyestutf dyed polyester fibres yellow shades of very good fastnessproperties.

EXAMPLE 3 50 parts of 4-ch1orophenol were melted and mixed at 100 C.with 3 parts of anhydrous potassium carbonate and 9 parts of4-bromo-5'-nitro-3-hydroxy-quinophthalone. This mixture was,subsequently heated to C. until in a sample no more starting substancecould be ascertained by thin-layer-chromatography. The me-lt was pouredin 200 parts of methanol. The dyestufl was suctionfiltered, washed anddried. 8 parts of 4-(4"-chlorophenoxy)-5'-nitro-3-hydroxy-quinophthaloneof the formula CHa were obtained melting at 360 C. The yield amounted to79.5% of the theory. The dyestufi dyed polyester fibers I yellow shadeshaving excellent fastness properties. HO

EXAMPLE 4 C 50 parts of 4-hydroxy-amsol were melted and mixed 5 i' with4 parts of anhydrous tributyl-amine and 9 parts of C H4-bromo-3-hydroxy-quinophthalone at 100 C. This mix- |e ture was,subsequently, heated to 150 C. until in a sample 0 no more startingsubstance was traceable. The melt was 10 were obtained melting at 273 C.The yield amounted to poured in 200 parts of methanol. The dyestuif wasdrawn 93% of the theory. The dyestuff dyed polyester fibres yeloif,washed and dried. 8 parts of 4-(4'-methoxy-phenoxy)- low shades havinggood fastness properties. 3-h d ox ino hth 1 th y r y qu p a one ofeformula EXAMPLE 6 150 parts of 2,5-dichloro-thiophenol, 7.5 parts ofpotas- OQOCH; sium hydroxide and 26 parts of 4 bromo-B-hydroxy- O 1quinophthalone were heated for 4 hours to 150 C. The (U; mixture was,subsequently, poured into 500 parts of meth- HO anol andsuction-filtered. The product was washed and dried. 31.5 parts of4-(2,5-dichlorophenylmercapto)-3- flg hydroxy-quinophthalone of theformula H 01 0 were obtained meltlng at 236 to 238 C. The yield ll 1amounted to 79% of the theory. The dyestuif dyed poly- Ho ester fibresyellow shades possessing excellent fastness properties. \3

EXAMPLE 5 H 150 parts of methanol, 7.5 parts of potassium hydroxide and26 parts of 4-bromo-3-hydroxy-quinophthalone were heated in an autoclaveto 150 C. until no more starting were obtained melting at 219 C. Theyield amounted substance was traceable in a sample. The content of theto 95% of the theory. The dyestuff dyed polyester fibres autoclave wassubsequently drawn off, washed with methgreenish yellow shades havingexcellent fastness properties. anol and dried. 21 parts of4-methoxy-3-hydroxy-quino- The following table lists further dyestuffsobtainable phthalone of the formula by the methods described in Examples1 to 6.

Starting substance Reaeted with- Dyestufi Shade4-bromo-3-hydroxy-quinophthalone 2-chlorophenol4-(2-ehlorophenoxy)-3hydroxyquinophthalone Yellow. D 4-ehloropl1eno14-(4-chlorophenoxy)-3-hydroxyquinophthalone- Do. D 3-hydr0xy-to1uene-.-.4-(3-methyl-phenoxy)-3-hydroxyquinophthalone- Do. D 4-bromophenol4-(4-bromophen0xy)'3-hydroxyquinophthalone".. Do. Dn 3-m'trophenol4-(3-nitropheuoxy)-3-hydroxyquinophthalone Greelrlilsh ye ow DnHydroqmnone 4-(4'-hydr0xy-pheuoxy)'3-hydroxyquinophthalone. Yellow D3-hydroxy-benzoie acid amide. 4-(3-amirillzfigbonyl-phenoxy)-3-hydroxy-Do.

qmnop one. Do Ethyleneglyeol4-(fl-hydroxy-ethoxy)-3-hydroxyquinophthalone Do. D Diethyleneglycol4-[fi-(B-hydroxy-ethoxy)-ethoxy]-3-hydroxy- Do.

quinophthalone. D 2-hydr0xy-pyridlne4-(2'-pyrldyl-oxy)-3-hyd.roxyquinophthalone Do. D Thiophenol4-phenyl-mercapto-3-hydroxyquiuophthalone Gleefilish ye ow. Dothydroxy-diphenylmethanm. 4-(4benzyl-phenoxy)3-hydroxyqulnophthaloneYellow. Do 3-hydroxy-pr0pion1t1ile... 1-(fiasyenoethoxy)-Zl-hydroxyquinophthalouone Do. Do Z-dimethylamino-ethauol--(fll-lciilmefiltigltlunino-ethoxy)-3-hydroxy- Do.

q nop a one. D Etlgleneglycol-monoethyl4-(fl-ethoxy-ethoxy)-3-hydroxyquluophthalone Do.

e er. D 2-chloro-ethan0l 4-(fl-chloro-ethoxy)-3-hydroxyquiuophthaloneDo. Do Hexandiol-(1,6) -(w-hydroxy-hexoxy)-3-hydroxyqu.iuophthaloue Do.Do Hexahydrobenzyl alcohol4-hexahydro-benzyloxy-(i-hydroxyquinophthalone Do. Do3-hydroxy-benzaldehyde- 4(3-Iormy1-phenoxy)-3-hydroxyqulnophthalon Do.Do 4-hydroxy-acetophen0ne 4-(4-a.cetyl-phenoxy)-3-hydroxyquinophthaloneDo. Do 4-hy1tllri)xybenz0ic acid4-(4"earbethoxy-phenoxy)-3-hydroxyquinophthalone-. Do.

et y es er. D 4-dimethyl-a.mino-phenol4-(4dimethylamino-phenoxy)-3-hydroxy- Do.

quinophthalone. D Thiophenol-Z-carboxylic acid 4- (2-ca.rbgxly-pheuylmereapto)-3-hydroxy- Do.

qumop B 0118. 4-ehloro-4-bromo-8-hydroxyquinophthalone Phenol4'-chloro+phenoxy-3-hydroxyquiuophthaloue Do.5-pheuyl-4-bromo-3-hydroxyqu.inophthalone 4-hydroxy-toluene 5-phenyll-14t-t(1 l-methyl-phenoxy)-3-hydroxy- Do.

qumop a one. 4,4,5,6',7-pentabromo-3-hydroxy- 4-ehlorophenol 4, 5, 6,7-tetrabromo-4-(4"-ch1or0phen0xy)-3- Do.

quinophthalone. hydroxy-quinophthaloue.4,6-dibromo-3-hydroxyqu.inophthalone 4-bromophenol6-bromo-4-(4-bromo-phenoxy)-3-hydroxyquinophthal- Do.

one. i 4chlor0'3-hydroxy-quiuophthalone. 4-hydroxyhenylether-4-(4-phenoxy-phenoxy)-3-hydroxyquinophthalone Do.4-bromo:3-hydr0xy-quinophthalone Dodecanol-(lg-dodeeyloxy-3-hydroxy-quinophthalone Do. Do- Dodeeanthiol-(1)4-dodeeyl-mereapto-Bhydroxy-quinophthalone Do. Do. 4-tert.-buty1-pheuol-4-(4-tert--butyl-phenoxy)-3-hyd.roxyquinophtha1one.. Do. Do.4-nonyl-thiopheuol 4(4'-nonyl-phenylmereapto)-3-hydroxyqu.iu0phthal- Do.

one. Do 4-chlorophenyl-B-hydroxy-4-(fl-(4'-ch1orophenyl-sulfony1)-ethoxy)-3-hydroxy- Do.

ethylsulfone. quinophthalone. Do 2-hydroxy-diphenyl4-(2-phenyl-phenoxy)-3-hydroxy-quinophthalone. Do. Do... Z-naphthol4-(2'-naphthoxy)-3-hydroxy-qu.inophtha1one Do. Do 2-ehloro-1-naphthol4-(2-ehloro-l-naphthoxy)-2-hydroxyquinophthalone. D0. D0.5-nitro-2-mereaptobenzimida-4-(5-nitro-beuzlmidazolyl-2-mercapto)-3-hydroxy- Do.

zol. quiuophthalone. Do 5-nitro-2-hydroxypyridine--.5-(5'-nitro-pyridyl-2-oxy)-3-hydroxyquinophthalone..- Do.

TABLE-Continued Starting substance Reacted with Dyestufl Shade4bro1no:B-hydroxy-quinophthalone fi-hydroxy-quinoline4-(chinolyl-6'-0xy)-3-hydroxy-quinophthalone Yellow. D2-mercapto-benzoxazol 4-(benzoxazolyl-2-mereapto)-3-hydroxyqu.inophthal-Do.

one. Do. -mereapto-1phenyltetrazol 4-(1'filgngl-tehfldyl-5'-mercapto)-3-hydroxy-quin- Do.

op a one. N-B-hydroxy-ethylmorpholine.4-(fl-N-morpholinyl-ethoxy)-3-hydroxyquinophthalono. Do. Do-2-mercapt0-benzthiazol4-(benzthiazolyl-2-mercapto)'3-hydroxy-quinophthal- Do.

one. Do. S-hydroxy-pyrene 4-(pyrenyl-3bxy)-3-hydroxy-quinophthalone Do.Do. l-hydroxy-anthracene4-(anthracenyl-1'-oxy)-3-hydroxy-quinopl1thalone- Do. Do.Hydroquinone-mono'fi- 4-[4-(fi-hydroxyethoxy)-phenoxy]-3-hydroxyquino-Do.

hydroxy-ethyl ether. phthalone. Do Pyrocatechol-mono-B-4-[2-(fi-hydroxy-ethoxy)-phenoxy]-3-hydroxy-quino- Do.

' hydroxy-ethyl ether. pthalone. Do 4-(fl-hydroxy ethoxy)-thio-4-[4'-(B-hydroxy-ethoxy)-phenylmercapto1-3-hydroxy- Do.

phenol. quinophthalone. Do- Resorcinol-monoaaflfi- 4-[3'-(a,afl,fl-tetrafiuoroethoxy)-phen0xy]-3-hydroxy- Do.

tetrafiuoroethyl ether. quinophthalone. Do 4-butoxy-phenol4-(4-butoxy-phenoxy)-3-hydroxy-qmnophthalone Do. Do- 4-fluorophenol4-(4'-fluoro-phenoxy)-3-hydroxy-quinophthalone Do. Do-Phlelrllfyl-fi-hydroxyethyb4-(B-phenylsnlionyl)-ethoxy3-hydroxy-quinophthal- Do.

s one. one. Do Mercapto-cyclohexane-eyclohexyl-mercapto-3-hydroxy-quinophthalone.-... Do.A-bromo-5,7-dlchloro-3-hydroxy-quinophthal- Phenol4-phenoxy-5,7-diehloro-3-hydroxy-quinophthalone-.... Do.

one.

We claim: 4. The dyestuff of the formula 1. A dyestuff of the formulaS--R 0 l Cl 1 H0 Zll S Ym c O I (HN 1 H 0 Ho C N wherein R is phenyl orphenyl substituted by one or two of the groups chlorine, bromine, alkylof 1 to 9 carbon 0 atoms or alkoxy of 1 to 4 carbon atoms, provided that6 branched alkyls or alkoxys are metaor parato one another, Z ishydrogen, chlorine or bromine, Y is hydrogen, chlorine, bromine, nitroor phenyl, m is an integer 1 to 4 R f Ct d (1 if Y is nitro or phenyl)and n is an integer 1 or 2. e erences e 2. A dyestuif according to claim1 wherein R is: phen- UNITED STATES PATENTS yl; phenyl substituted byone or two of the groups chlo- 40 3,107,261 10/1963 Gerber 260453 rine,bromine, unbranched alkyl of 1 to 9 carbon atoms or nnbranched alkoxy of1 to 4 carbon atoms; or phenyl DONALD DAUS, primary Examiner substitutedby one of the groups branched alkyl of 4 to 9 carbon atoms or branchedalkoxy of 4 carbon atoms. US. Cl. X.R.

3. The dyestuff of the formula 260-289 QP O llHo

